CN108982286A - The separation and quantitative approach of different preservation state Soluble Organic Matters in mud shale - Google Patents
The separation and quantitative approach of different preservation state Soluble Organic Matters in mud shale Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
Abstract
The present invention relates to the separation and quantitative approach of preservation state Soluble Organic Matters different in mud shale, comprising: mud shale core sample is fully ground simultaneously low temperature drying；Soxhlet type is carried out to mud shale sample with organic solvent, separation Group Component is simultaneously quantitative；Alkaline hydrolysis processing is carried out to extracting residue, and soxhlet type is carried out to alkaline hydrolysis residue, separation Group Component is simultaneously quantitative；Acidolysis processing is carried out to the alkaline hydrolysis residue after extracting, and soxhlet type is carried out to acid hydrolysis residue, separation Group Component is simultaneously quantitative；The processing of HCl/HF acid-mixed acid is carried out to the acid hydrolysis residue after extracting, and soxhlet type is carried out to nitration mixture acid hydrolysis residue, separation Group Component is simultaneously quantitative；It calculates organic component obtained by every step and accounts for each Group Component mass fraction in the mass fraction and every step gained organic component of rock.Compared with prior art, the present invention has the advantages that high-efficient, at low cost, data are congruent.
Description
Technical field
It, can be dissolved with more particularly, to preservation states different in a kind of mud shale the present invention relates to petroleum and gas geology and exploration development field
The separation and quantitative approach of machine matter.
Background technique
Soluble Organic Matter is the important component in mud shale, and quantitative study difference preservation state Soluble Organic Matter is to oil gas
The researchs such as resource assessment, shale oil mobility, hydrocarbon primary rock producing hydrocarbon mechanism and Oil And Gas Occurrence mechanism are of great significance.Many institute's weeks
Know, mud shale is made of detrital mineral (quartz and feldspar etc.), clay mineral, carbonate rock and organic matter etc., and various substances are special
The difference of sign and its between different interaction, causing mud shale is a complicated system, and then leads to Soluble Organic Matter
Preservation in mud shale has otherness and hierarchy.The separation and quantitative skill of different preservation state Soluble Organic Matters in mud shale
Art can effective quantitative study difference preservation state Soluble Organic Matter the features such as absolute content, relative scale, race's composition, for oil
Gas exploration developmental research provides strong experimental technique support.
It is organic solvent direct extraction that the most common method of Soluble Organic Matter in mud shale is obtained in petroleum geology research, most
Common extractant is chloroform or methylene chloride, the Soluble Organic Matter that methylene chloride extracts mainly with free state preservation in
Hole, which is neutralized, is adsorbed in mineral surfaces with physical adsorption way, and there are also quite a few chemical bonding state Soluble Organic Matters to obtain
It takes.With going deep into for research, occur many new methods in extracting mode and extraction solvent, as MAC ternary agent extracting,
CS2The superpower mix reagent extracting of/NMP, CO2(modifying agent is added) supercritical fluid extraction, accelerated solvent extraction (ASE) etc., but its
The Soluble Organic Matter of extraction only can be variant in quantity and component, however, in mud shale between organic matter and inorganic mineral
There is complicated interaction, the two can mutually be tied by physical absorption, chemical bonding, lattice package with modes such as Inter layer adsorptions
It closes.Clay mineral due to surface charge presence and huge specific surface area and have very strong chemical activity, can be in mineral table
Face or interlayer effectively adsorb organic matter.When recrystallization occurs for carbonate mineral, mineral lattice can be by the organic matter packet of surrounding
It wraps to form package organic matter." kerogen " can take Soluble Organic Matter in by the similar principle that mixes.Therefore, it only uses
The method of organic solvent direct extraction is can not to determine Soluble Organic Matter true preservation position and mode in mud shale, right
The supporting environment of Soluble Organic Matter has significant limitation in research mud shale.
It interacts in view of organic matter and mineral exist, the method that organic solvent extracting and chemical treatment combine should be
Preferable selection.Mud shale extracts to obtain in hole after free state Soluble Organic Matter through organic solvent, can by succession chemistry at
Reason method destroys the inorganic mineral in mud shale, gradually releases reference state Soluble Organic Matter and is studied, at common chemistry
Reason method is HCl acidolysis and HCl/HF acidolysis.The carbonate mineral in mud shale can be effectively destroyed using HCl, to discharge
It is carbonated the Soluble Organic Matter of salt mineral combination out.The silicic acid in mud shale can be effectively destroyed using a certain proportion of HCl/HF
Salt mineral make the bonding relationships between Soluble Organic Matter and mineral disintegrate and be released.Common alkali is gone back in soil organism research
Solution reaction (KOH aqueous slkali) can be released effectively the aliphatic organic matter that ester output bond is closed.Research shows that KOH aqueous slkali can be with
So that the interlamination region of montmorillonite is collapsed, and the interlayer of montmorillonite contains organic matter more in mud shale, with the collapsing of interlamination region, this portion
Divide the available release of Soluble Organic Matter, but alkaline hydrolysis processing yet there are no system report applied to the method for mud shale.Organic solvent
Extracting the core concept for combining method with chemical treatment is since the chemical property of mineral is different, using specific chemical treatment
Method can be obtained by the Soluble Organic Matter combined with inorganic minerals different in mud shale, be a kind of ideal research side
Method, but do not form unified standard separation process at present.
Chinese patent CN106769618A discloses a kind of separating and extracting process of free hydrocarbon in mud shale, using dichloromethane
Alkane, which passes through extraction twice at normal temperature and is centrifugated extraction free hydrocarbon, is better than petroleum since methylene chloride polarity is weaker than chloroform
Ether, can not only guarantee free hydrocarbon sufficiently, quick release come out, but also can control the precipitation of absorption hydro carbons, and methylene chloride is close
Spend smaller, when centrifuge separation can reduce the emersion point of insoluble free organic matter (kerogen).Adsorbed hydrocarbons in shale petroleum resources
It is the emphasis for needing to pay close attention to, which does not consider adsorbed hydrocarbons just for free hydrocarbon.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide different in a kind of mud shale
The separation and quantitative approach of preservation state Soluble Organic Matter.
The purpose of the present invention can be achieved through the following technical solutions:
The separation and quantitative approach of different preservation state Soluble Organic Matters in mud shale, using following steps:
(1) mud shale core is fully ground simultaneously low temperature drying；
(2) soxhlet type is carried out to mud shale core with organic solvent, separation Group Component is simultaneously quantitative；
(3) alkaline hydrolysis processing is carried out to extracting residue, and soxhlet type is carried out to alkaline hydrolysis residue, separation Group Component is simultaneously quantitative；
(4) acidolysis processing is carried out to the alkaline hydrolysis residue after extracting, and soxhlet type is carried out to acid hydrolysis residue, separate Group Component
And it is quantitative；
(5) using the acid hydrolysis residue after nitration mixture processing extracting, and soxhlet type, separating family group are carried out to nitration mixture acid hydrolysis residue
Divide and quantifies；
(6) mass fraction (chloroform bitumen " A ") and gained organic component that organic component obtained by each step accounts for rock are calculated
In each Group Component mass fraction, complete the separation and quantitative to organic matters different in mud shale.
Mud shale core is ground to 80 mesh or more by step (1), and temperature is not higher than in 50 DEG C and is dried.
Step (2) uses following methods: the mud shale core after grinding drying being placed in Soxhlet extractor, with dichloromethane
Alkane extracts 72h as solvent in water-bath, after gained extract precipitation bitumens matter, isolates saturated hydrocarbons, aromatic hydrocarbons and nonhydrocarbon, mud
Shale core weighs no less than 50 grams before extracting.
Step (3) uses following methods: KOH and methyl alcohol mixed liquor is added into extracting residue, wherein the concentration of KOH solution
For 6wt%, the volume ratio of methanol and water is 9:1, the alkaline hydrolysis 16h under 60 DEG C and magnetic agitation in methanol solution, with 3000 revolutions per seconds
Solidliquid mixture is centrifuged 15 minutes by centrifuge, and alkali solution liquid and alkaline hydrolysis residue after being reacted, alkaline hydrolysis residue add deionized water
It washs and is centrifugated repeatedly, until residue is washed till neutrality, merges alkali solution liquid and centrifugate, be first 2-3 with salt acid for adjusting pH value, so
It is extracted repeatedly with methylene chloride afterwards, obtains dichloromethane extract, be fully ground after neutral residue low temperature drying being washed till,
It is taken out using methylene chloride as solvent in Soxhlet extraction device and mentions 72h, obtained methylene chloride extract and residue, methylene chloride is extracted
Liquid and extract merge, and after precipitation bitumens matter, isolate saturated hydrocarbons, aromatic hydrocarbons and nonhydrocarbon.
Step (4) uses following methods: concentration is added into alkaline hydrolysis residue as the hydrochloric acid solution of 6M, is placed in magnetic agitation instrument
On, solidliquid mixture is centrifuged 15 minutes, acid hydrolysis solution and acid after being reacted by 60 DEG C of acidolysis 16h with 3000 revolutions per seconds of centrifuges
Residue is solved, acid hydrolysis residue adds deionized water to wash and be centrifugated repeatedly, until residue is washed till neutrality, merges acid hydrolysis solution and centrifugation
Liquid is extracted repeatedly with methylene chloride, obtains dichloromethane extract, is fully ground after being washed till neutral residue low temperature drying,
Using methylene chloride as solvent extraction 72h in Soxhlet extraction device, methylene chloride extract and residue are obtained, methylene chloride is extracted
It takes liquid and extract to merge, after precipitation bitumens matter, isolates saturated hydrocarbons, aromatic hydrocarbons and nonhydrocarbon.
Step (5) uses following methods: the mixed solution of HCl and HF being added into acid hydrolysis residue, wherein HCl solution is dense
Degree is 12M, and the concentration of HF solution is 40wt%, and volume ratio between the two is 1:1, the acidolysis 16h under 60 DEG C and magnetic agitation,
Solidliquid mixture is centrifuged 15 minutes with 3000 revolutions per seconds of centrifuges, acid hydrolysis solution and acid hydrolysis residue after being reacted, acid hydrolysis residue
Add deionized water to wash and be centrifugated repeatedly, until residue is washed till neutrality, merges acid hydrolysis solution and centrifugate, repeatedly with methylene chloride
Extraction, obtains dichloromethane extract.It is fully ground after neutral residue low temperature drying being washed till, with two in Soxhlet extraction device
Chloromethanes obtains methylene chloride extract and residue as solvent extraction 72h, and dichloromethane extract and extract are merged,
After precipitation bitumens matter, saturated hydrocarbons, aromatic hydrocarbons and nonhydrocarbon are isolated.
Residue after each step extracting is weighed through balance.
Group component separation uses column chromatography, obtained extract, the saturated hydrocarbons isolated, aromatic hydrocarbons, nonhydrocarbon in each step
It weighs with the balance of asphalitine a ten thousandth precision.
The quality calculation method for the non-hydrocarbon component that Group component separation goes out in step (2)-(5) are as follows:
GiN=GiC-GiS-GiA-GiB
In formula:
GiN- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component nonhydrocarbon quality, g；
GiCWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
GiS- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component saturated hydrocarbons quality, g；
GiA- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component aromatic hydrocarbons quality, g；
GiBWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component studies on asphaltene, g in 3,4,5.
Organic component obtained by each step accounts for the mass fraction calculation method of rock in step (6) are as follows:
Xi=Gi/ M*100%
In formula:
XiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, organic component accounts for the mass fraction of rock in 3,4,5, with
Percentage indicates；
GiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
M-primary sample quality, g.
Each Group Component mass fraction calculation method in organic component obtained by each step in step (6) are as follows:
Xij=Gj/Gi* 100%
In formula:
XijWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, in 3,4,5 gained organic components, j S, A, N, B are replaced
When, the mass fraction of saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon and asphaltene is respectively indicated, is expressed as a percentage；
GiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
Gj- j S, A, N respectively indicate the quality of saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon and asphaltene, g when B is replaced.
The application had both used methylene chloride to directly obtain the Soluble Organic Matter of free state as organic extraction agent, while gradually
With the Soluble Organic Matter of the adsorptions such as KOH solution release clay mineral, carbonate mineral is destroyed with HCl and discharges preservation in it
In Soluble Organic Matter, it is solvable organic to obtain dissolving in " kerogen " finally to destroy silicate mineral with HCl/HF nitration mixture
Matter.
Compared with prior art, the present invention selects methylene chloride as organic extraction agent first, and small toxicity can be adequately
The free state Soluble Organic Matter in mud shale in hole and the Soluble Organic Matter of mineral surfaces physical absorption are extracted, while not being broken
The Nomenclature Composition and Structure of Complexes of bad mud shale.Secondly, can targetedly destroy clay mineral surfaces externally and internally and Soluble Organic Matter with KOH solution
Between chemical bond, to obtain this part chemical adsorption states Soluble Organic Matter, while to the structure of mud shale Minerals without bright
It is aobvious to destroy.Then, can effectively destroy carbonate mineral with HCl, to other mineral act on it is unobvious, thus discharge preservation in
Soluble Organic Matter in carbonate mineral.Finally, selecting HF that can dissolve silicic acid mineral, " kerogen " is obtained, to extract
Solubilised state Soluble Organic Matter in " kerogen " out.Finally, the present invention uses organic solvent extracting-alkaline hydrolysis-HCl acidolysis-HCl/
It is solvable effectively can gradually to isolate corresponding extracting Soluble Organic Matter, alkaline hydrolysis for the continuous processing process of HF nitration mixture acidolysis "
Organic matter, acidolysis Soluble Organic Matter and HCl/HF nitration mixture acidolysis Soluble Organic Matter, different preservation states can in quantitative analysis mud shale
Organic matter total amount, Group Component and the total hydrocarbon feature of molten organic matter specify in mud shale the opposite of different preservation state Soluble Organic Matters
Content/ratio, organic component feature.
Detailed description of the invention
Fig. 1 is flow chart of the invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
As shown in FIG. 1, FIG. 1 is the separation of preservation state Soluble Organic Matters different in mud shale of the invention and quantitative approach streams
Cheng Tu.In step 101, mud shale sample will be fully ground to more than 80 mesh, after low temperature (temperature is not higher than 50 DEG C) drying always
Drying is kept, process enters 102.
In step 102, the sample that step 101 obtains quantitatively is weighed with balance, it is 50 grams many.Weighed sample is placed in
In Soxhlet extractor, using methylene chloride as solvent extraction 72 hours, methylene chloride extract and extracting residue are obtained.To extracting
Residue afterwards is weighed.It is transferred to after extract is concentrated in the weighing bottle of constant weight, evaporates into after doing and weigh.After weighing
Extract precipitation bitumens matter, and it is quantitative to asphalitine.Column chromatography is used to isolate the extract after precipitation bitumens matter full
And quantitative with the balance of a ten thousandth precision with hydrocarbon, aromatic hydrocarbons, non-hydrocarbon component, process enters step 103.
In step 103, it is transferred to residue is extracted in step 102 in 500ml round-bottomed flask, 400ml 6%KOH/ is added
Methyl alcohol mixed liquor (MeOH/H2O 9:1, v:v), is placed on magnetic agitation instrument, with 60 DEG C of temperature alkaline hydrolysis 16h.After alkaline hydrolysis,
Solidliquid mixture is centrifuged 15 minutes with 3000 revolutions per seconds of centrifuges, alkali solution liquid and residue after being reacted.Alkaline hydrolysis residue adds
Ionized water is washed and is centrifugated repeatedly, until residue is washed till neutrality.Merge alkali solution liquid and centrifugate, be 2-3 with HCl tune pH value,
It is extracted again with methylene chloride.It is extracted repeatedly with methylene chloride, obtains dichloromethane extract.The residue for being washed till neutral is low
It is fully ground after temperature drying, using methylene chloride as solvent extraction 72 hours in Soxhlet extraction device, obtains methylene chloride extracting
Liquid and residue.It weighs to the residue after extracting.Dichloromethane extract and extract are merged, are transferred to after concentration permanent
In the weighing bottle of weight, evaporates into after doing and weigh.To the extract precipitation bitumens matter after weighing, and it is quantitative to asphalitine.To precipitating
Extract after asphalitine isolates saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon component using column chromatography, and with the balance of a ten thousandth precision
Quantitative, process enters step 104.
In step 104, the alkaline hydrolysis residue after extracting in step 103 is moved in 500ml round-bottomed flask, 400ml 6M is added
HCl solution is placed on magnetic agitation instrument, with 60 DEG C of temperature acidolysis 16h.After acidolysis, it will be consolidated with 3000 revolutions per seconds of centrifuges
Liquid mixture is centrifuged 15 minutes, acid hydrolysis solution and residue after being reacted.Acid hydrolysis residue adds deionized water to wash and be centrifuged repeatedly
Separation, until residue is washed till neutrality.Merge acid hydrolysis solution and centrifugate, is extracted repeatedly with methylene chloride, obtain dichloromethane extract.
It is fully ground after neutral residue low temperature drying being washed till, it is small using methylene chloride as solvent extraction 72 in Soxhlet extraction device
When, obtain methylene chloride extract and residue.It weighs to the residue after extracting.Dichloromethane extract and extract are closed
And be transferred to after concentration in the weighing bottle of constant weight, it evaporates into after doing and weighs.To the extract precipitation bitumens matter after weighing, and
It is quantitative to asphalitine.Saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon component are isolated using column chromatography to the extract after precipitation bitumens matter, and
Quantitative with the balance of a ten thousandth precision, process enters step 105.
In step 105, the acid hydrolysis residue after extracting in step 104 is transferred in 500ml polytetrafluoroethylplastic plastic container,
400ml HCl 12M/HF 40% (1/1v/v) solution is added, is placed on magnetic agitation instrument, with 60 DEG C of temperature acidolysis 16h.Acid
After solution, solidliquid mixture is centrifuged 15 minutes with 3000 revolutions per seconds of centrifuges, acid hydrolysis solution and residue after being reacted.Acid
Solution residue adds deionized water to wash and be centrifugated repeatedly, until residue is washed till neutrality.Merge acid hydrolysis solution and centrifugate, uses dichloromethane
Alkane extracts repeatedly, obtains dichloromethane extract.It is fully ground after neutral residue low temperature drying being washed till, in Soxhlet extraction device
In using methylene chloride as solvent extraction 72 hours, obtain methylene chloride extract and residue.Residue after extracting is claimed
Weight.Dichloromethane extract and extract are merged, are transferred to after concentration in the weighing bottle of constant weight, evaporates into after doing and weighs.
To the extract precipitation bitumens matter after weighing, and it is quantitative to asphalitine.Column chromatography is used to the extract after precipitation bitumens matter
Saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon component are isolated, and quantitative with the balance of a ten thousandth precision, process enters step 106.
In step 106, calculates organic component obtained by every step and account for obtained by mass fraction (chloroform bitumen " A ") and the every step of rock
Each Group Component mass fraction in organic component.The wherein nonhydrocarbon group that Group component separation goes out in step 2, step 3, step 4 and step 5
The quality calculation method divided are as follows:
GiN=GiC-GiS-GiA-GiB
In formula:
GiN- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component nonhydrocarbon quality, g；
GiCWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
GiS- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component saturated hydrocarbons quality, g；
GiA- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component aromatic hydrocarbons quality, g；
GiBWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component studies on asphaltene, g in 3,4,5；
Organic component obtained by every step accounts for the mass fraction calculation method of rock are as follows:
Xi=Gi/ M*100%
In formula:
XiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, organic component accounts for the mass fraction of rock in 3,4,5, with
Percentage indicates；
GiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
M-primary sample quality, g.
Each Group Component mass fraction calculation method in organic component obtained by every step are as follows:
Xij=Gj/Gi* 100%
In formula:
XijWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, in 3,4,5 gained organic components, j S, A, N, B are replaced
When, the mass fraction of saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon and asphaltene is respectively indicated, is expressed as a percentage；
GiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
Gj- j S, A, N respectively indicate the quality of saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon and asphaltene, g when B is replaced.
Here is more specifical embodiment, further illustrates technical solution of the present invention.
Embodiment 1
Choose the mud page that lower sub- section (Es3x) depth of Dongying Sag, Jiyang Depression PALEOGENE SHAHEJIE FORMATION sand three is 3339.6m
Rock sample product, the separation of different preservation state Soluble Organic Matters carries out as follows with quantitative approach in the sample；
Mud shale sample will be fully ground to more than 80 mesh by step A, after low temperature (temperature is not higher than 50 DEG C) drying always
Drying is kept, for use；
Step B quantitatively weighs 85.27 grams of samples with balance and is placed in Soxhlet extractor, is taken out using methylene chloride as solvent
It mentions 72 hours, obtains methylene chloride extract and extracting residue.It weighs to the residue after extracting.Extract is concentrated
It is transferred in the weighing bottle of constant weight afterwards, evaporates into after doing and weigh (table 1).To the extract precipitation bitumens matter after weighing, and it is right
Asphalitine is quantitative (table 1).Saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon component are isolated using column chromatography to the extract after precipitation bitumens matter,
And it is quantitative (table 1) with the balance of a ten thousandth precision；
Residue after extracting in step B is transferred in 500ml round-bottomed flask by step C, and 400ml 6%KOH/ first is added
Alcohol mixed liquor (MeOH/H2O 9:1, v:v), is placed on magnetic agitation instrument, with 60 DEG C of temperature alkaline hydrolysis 16h.After alkaline hydrolysis, use
Solidliquid mixture is centrifuged 15 minutes by 3000 revolutions per seconds of centrifuges, alkali solution liquid and residue after being reacted.Alkaline hydrolysis residue add from
Sub- water is washed and is centrifugated repeatedly, until residue is washed till neutrality.Merge alkali solution liquid and centrifugate, is 2-3 with HCl tune pH value, then
It is extracted with methylene chloride.It is extracted repeatedly with methylene chloride, obtains dichloromethane extract.Neutral residue low temperature will be washed till
It is fully ground after drying, using methylene chloride as solvent extraction 72 hours in Soxhlet extraction device, obtains methylene chloride extract
And residue.It weighs to the residue after extracting.Dichloromethane extract and extract are merged, constant weight is transferred to after concentration
Weighing bottle in, evaporate into it is dry after weigh (table 1).(table is quantified to the extract precipitation bitumens matter after weighing, and to asphalitine
1).Saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon component are isolated using column chromatography to the extract after precipitation bitumens matter, and use a ten thousandth
The balance of precision is quantitative (table 1)；
Step D moves to the alkaline hydrolysis residue after extracting in step C in 500ml round-bottomed flask, and it is molten that 400ml 6M HCl is added
Liquid is placed on magnetic agitation instrument, with 60 DEG C of temperature acidolysis 16h.After acidolysis, solid-liquid is mixed with 3000 revolutions per seconds of centrifuges
It closes object to be centrifuged 15 minutes, acid hydrolysis solution and residue after being reacted.Acid hydrolysis residue adds deionized water to wash and be centrifugated repeatedly,
Neutrality is washed till to residue.Merge acid hydrolysis solution and centrifugate, is extracted repeatedly with methylene chloride, obtain dichloromethane extract.It will wash
It is fully ground after to neutral residue low temperature drying, using methylene chloride as solvent extraction 72 hours in Soxhlet extraction device, obtains
To methylene chloride extract and residue.It weighs to the residue after extracting.Dichloromethane extract and extract are merged, it is dense
It is transferred to after contracting in the weighing bottle of constant weight, evaporates into after doing and weigh (table 1).To the extract precipitation bitumens matter after weighing, and
It is quantitative (table 1) to asphalitine.Saturated hydrocarbons, aromatic hydrocarbons, nonhydrocarbon group are isolated using column chromatography to the extract after precipitation bitumens matter
Point, and it is quantitative (table 1) with the balance of a ten thousandth precision；
Acid hydrolysis residue after extracting in step D is transferred in 500ml polytetrafluoroethylplastic plastic container by step E, is added
400ml HCl 12M/HF 40% (1/1v/v) solution, is placed on magnetic agitation instrument, with 60 DEG C of temperature acidolysis 16h.Acidolysis knot
Solidliquid mixture is centrifuged 15 minutes, acid hydrolysis solution and residue after being reacted by Shu Hou with 3000 revolutions per seconds of centrifuges.Acidolysis is residual
Slag adds deionized water to wash and be centrifugated repeatedly, until residue is washed till neutrality.Merge acid hydrolysis solution and centrifugate, it is anti-with methylene chloride
Multiple extraction, obtains dichloromethane extract.Be fully ground after neutral residue low temperature drying will be washed till, in Soxhlet extraction device with
Methylene chloride obtained methylene chloride extract and residue as solvent extraction 72 hours.It weighs to the residue after extracting.It will
Dichloromethane extract and extract merge, and are transferred in the weighing bottle of constant weight after concentration, evaporate into after doing and weigh (table 1).
To the extract precipitation bitumens matter after weighing, and it is quantitative (table 1) to asphalitine.Column layer is used to the extract after precipitation bitumens matter
Analysis method isolates saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon component, and quantitative (table 1) with the balance of a ten thousandth precision；
Step F, calculate organic component obtained by every step account for rock mass fraction (chloroform bitumen " A ") and every step obtained by it is organic
Each Group Component mass fraction (table 2) in component.
The quantity of chloroform bitumen obtained by each step of table 1 and each Group Component
The mass fraction of each step chloroform bitumen " A " of 2 table of table 1 and each Group Component
Continuous processing process of the selected sample Jing Guo " extracting-alkaline hydrolysis-HCl acidolysis-HCl/HF acidolysis ", has obtained phase therewith
Extracting Soluble Organic Matter, alkaline hydrolysis Soluble Organic Matter, acidolysis Soluble Organic Matter and the HF acidolysis Soluble Organic Matter answered, but quantitatively
Have differences (table 1, table 2).Extracting Soluble Organic Matter quantity is 0.56109g, accounts for the 67.50% of total Soluble Organic Matter, alkaline hydrolysis can
It is 0.09504g dissolved with machine prime number amount, accounts for the 11.48% of total Soluble Organic Matter, acidolysis Soluble Organic Matter quantity is 0.03481g,
Mean value is 3.34mg, and the solvable acidolysis organic matter quantity of 4.20%, HF for accounting for total Soluble Organic Matter is 0.13924g, and accounting for always can be dissolved with
The 16.82% of machine matter.As can be seen that extractable organic matter (EOM) is the main occurrence form of Soluble Organic Matter, Soluble Organic Matter totality is accounted for
67.50%, the Soluble Organic Matter that subsequent chemistry is handled accounts for overall 32.5%.
In variant preservation state Soluble Organic Matter, the relative amount difference of Group Component is very big (table 1, table 2).Extractable organic matter (EOM)
In, saturated hydrocarbons is main component, accounts for the 61.87% of extracting Soluble Organic Matter total amount.In alkaline hydrolysis Soluble Organic Matter, nonhydrocarbon
(58.61%) and pitch (28.84%) becomes main component.Non- hydrocarbon content highest (70.35%) in acidolysis Soluble Organic Matter.HF
In acidolysis Soluble Organic Matter, asphalitine (82.04%) be increased significantly, and become main component, secondly be nonhydrocarbon (16.19%), be satisfied
It is very low with hydrocarbon (0.81%) and aromatic hydrocarbons (0.96%) content.From the results, it was seen that the weakly polar components master such as saturated hydrocarbons and aromatic hydrocarbons
To exist in the form of extractable organic matter (EOM), and ratio of the non-hydrocarbon and asphaltene isopolarity component in reference state increases.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. the separation and quantitative approach of different preservation state Soluble Organic Matters in mud shale, which is characterized in that this method is using following
Step:
(1) mud shale core is fully ground simultaneously low temperature drying；
(2) soxhlet type is carried out to mud shale core with organic solvent, separation Group Component is simultaneously quantitative；
(3) alkaline hydrolysis processing is carried out to extracting residue, and soxhlet type is carried out to alkaline hydrolysis residue, separation Group Component is simultaneously quantitative；
(4) acidolysis processing is carried out to the alkaline hydrolysis residue after extracting, and soxhlet type is carried out to acid hydrolysis residue, separate Group Component and is determined
Amount；
(5) using the acid hydrolysis residue after nitration mixture processing extracting, and soxhlet type is carried out to nitration mixture acid hydrolysis residue, separation Group Component is simultaneously
It is quantitative；
(6) it calculates organic component obtained by each step and accounts for each Group Component quality point in the mass fraction and gained organic component of rock
Number completes the separation and quantitative to organic matters different in mud shale.
2. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, mud shale core is ground to 80 mesh or more by step (1), and temperature is not higher than in 50 DEG C and is dried.
3. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, step (2) uses following methods: the mud shale core after grinding drying is placed in Soxhlet extractor, with methylene chloride
It is extracted in water-bath 72 hours as solvent, after gained extract precipitation bitumens matter, isolates saturated hydrocarbons, aromatic hydrocarbons and nonhydrocarbon.
4. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, step (3) uses following methods: KOH and methyl alcohol mixed liquor, the alkali under 60 DEG C and magnetic agitation is added into extracting residue
Solve 16h, centrifugal treating reacted after alkali solution liquid and alkaline hydrolysis residue, alkaline hydrolysis residue adds deionized water to wash repeatedly and is centrifuged point
From until residue is washed till neutrality, merging alkali solution liquid and centrifugate, first adjusting pH value with HCl is 2-3, then repeatedly with methylene chloride
Extraction, obtains dichloromethane extract, is fully ground after being washed till neutral residue low temperature drying, with two in Soxhlet extraction device
Chloromethanes, which is taken out, mentions 72h as solvent, obtains methylene chloride extract and residue, dichloromethane extract and extract are merged,
After precipitation bitumens matter, saturated hydrocarbons, aromatic hydrocarbons and nonhydrocarbon are isolated.
5. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, step (4) uses following methods: HCl solution is added into alkaline hydrolysis residue, is placed on magnetic agitation instrument, 60 DEG C of acidolysis
16h, centrifugal treating reacted after acid hydrolysis solution and acid hydrolysis residue, acid hydrolysis residue adds deionized water to wash repeatedly and is centrifuged point
From, until residue is washed till neutrality, merges acid hydrolysis solution and centrifugate, extracted repeatedly with methylene chloride, obtain dichloromethane extract, it will
It is fully ground after being washed till neutral residue low temperature drying, using methylene chloride as solvent extraction 72h in Soxhlet extraction device, obtains
Methylene chloride extract and residue merge dichloromethane extract and extract, after precipitation bitumens matter, isolate saturated hydrocarbons,
Aromatic hydrocarbons and nonhydrocarbon.
6. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, step (5) uses following methods: the mixed solution of HCl and HF is added into acid hydrolysis residue, under 60 DEG C and magnetic agitation
Acidolysis 16h, centrifugal treating reacted after acid hydrolysis solution and acid hydrolysis residue, acid hydrolysis residue adds deionized water to wash and be centrifuged repeatedly
Separation merges acid hydrolysis solution and centrifugate, is extracted repeatedly with methylene chloride, obtain dichloromethane extract until residue is washed till neutrality.
It is fully ground after neutral residue low temperature drying being washed till, using methylene chloride as solvent extraction 72h in Soxhlet extraction device, obtains
To methylene chloride extract and residue, dichloromethane extract and extract are merged, after precipitation bitumens matter, isolate saturation
Hydrocarbon, aromatic hydrocarbons and nonhydrocarbon.
7. the separation of different preservation state Soluble Organic Matters and quantitative square in mud shale according to claim 1 to 6
Method, which is characterized in that the residue after each step extracting is weighed through balance, and Group component separation uses column chromatography in each step, obtains
To extract, isolate saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon and asphaltene a ten thousandth precision balance weighing.
8. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, the quality calculation method for the non-hydrocarbon component that Group component separation goes out in step (2)-(5) are as follows:
GiN=GiC-GiS-GiA-GiB
In formula:
GiN- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component nonhydrocarbon quality, g；
GiCWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
GiS- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component saturated hydrocarbons quality, g；
GiA- i with 2,3,4,5 replace when, respectively indicate step 2, in 3,4,5 in organic component aromatic hydrocarbons quality, g；
GiBWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component studies on asphaltene, g in 3,4,5.
9. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, organic component obtained by each step accounts for the mass fraction calculation method of rock in step (6) are as follows:
Xi=Gi/ M*100%
In formula:
XiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, organic component accounts for the mass fraction of rock in 3,4,5, with percentage
Number indicates；
GiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
M-primary sample quality, g.
10. the separation and quantitative approach of different preservation state Soluble Organic Matters, feature in mud shale according to claim 1
It is, each Group Component mass fraction calculation method in organic component obtained by each step in step (6) are as follows:
Xij=Gj/Gi* 100%
In formula:
XijWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, in 3,4,5 gained organic components, j S, A, N, when B is replaced,
The mass fraction for respectively indicating saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon and asphaltene, is expressed as a percentage；
GiWhen-i is replaced with 2,3,4,5, step 2 is respectively indicated, the quality of organic component, g in 3,4,5；
Gj- j S, A, N respectively indicate the quality of saturated hydrocarbons, aromatic hydrocarbons, non-hydrocarbon and asphaltene, g when B is replaced.
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